US3856767A - Polymerisation process - Google Patents

Polymerisation process Download PDF

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US3856767A
US3856767A US00245193A US24519372A US3856767A US 3856767 A US3856767 A US 3856767A US 00245193 A US00245193 A US 00245193A US 24519372 A US24519372 A US 24519372A US 3856767 A US3856767 A US 3856767A
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vinyl chloride
seed
polymer
polymerisation
resin
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A Sturt
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F259/00—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00
    • C08F259/02—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine
    • C08F259/04—Macromolecular compounds obtained by polymerising monomers on to polymers of halogen containing monomers as defined in group C08F14/00 on to polymers containing chlorine on to polymers of vinyl chloride

Definitions

  • the present invention relates to a process for the production of vinyl chloride polymers by free radical polymerisation.
  • vinyl chloride polymer is meant throughout this specification polyvinyl chloride or a copolymer of vinyl chloride containing a major proportion of vinyl chloride and preferably not more than 20% by wt of copolymerisable materials.
  • Such polymers are obtained by the polymerisation of vinyl chloride monomer, which expression will be used hereafter to refer to vinyl chloride itself or a mixture of vinyl chloride with a copolymerisable compound or compounds in such a proportion that on polymerisation one obtains a vinyl chloride polymer as defined above.
  • Typical copolymerisable materials are acrylonitrile; vinyl acetate; olefins such as vinylidene chloride ethylene, propylene, isobutene and 4-methyl pentenel; acrylate and methacrylate esters, e.g., methyl methacrylate; and fumarate and maleate esters.
  • Vinyl chloride polymers have been produced having widely different crystallinities and as a result their properties have differed.
  • the percentage crystallinity of a polymer may be measured according to the method described in British patent specification No. 847,676. The method used in that patent is described as follows:
  • a sample of the polymer isobtained in the form of a thin sheet (about 0.003 thick) either by pressing at 160C or (if more convenient) by casting from solution in tetrahydrofuran on to a glass plate. After the sheet has beenannealed by heating for 3 hours at 150C and cooling slowly to room temperature in order to crystallise it to the maximum extent, it is mounted in a cylindrical X-ray diffraction camera normal to the beam, and an X-ray diffraction photograph is obtained using copper Ka radiation which has been. filtered so that only the Ka radiation is used. The variation of intensity with Bragg angle of the photograph is obtained by making a microphotometer traverse along the equator of the photograph.
  • the drawing accompanying the Complete Specification of British Pat. No. 847,676 shows a curve BCDEFGJ obtained for a sample of crystalline polyvinyl chloride. Also shown in this drawing is a curve BDFJ for an amorphous sample taken from the drawing accompanying the Provisional Specification of British Pat. No. 847,676.
  • the curve for the amorphous sample is chosen so that its trough just touches the curve BCDEFGJ at the point D, where it is assumed that there is no crystalline diffraction, and so that it fits the curve BCDEFGJ at high and low angles.
  • the straight line B] indicates the background level of intensity and the area below this line is ignored when calculating the crystallisability of the sample.
  • the percentage crystallisability of the sample to which the curve BCDEFGJ relates is equal to l00X/A X where A is the area bounded by the straight line B] and the curve for the amorphous sample and where X is the sum of the areas between the curve for the crystalline sample and the curve for the amorphous sample.
  • the percentage crystallinity of the sample to which the curve BCDEFGJ relates is thus approximately 25%
  • the accompanying FIG. 1 is a copy of the drawing accompanying the Complete Specification of British Pat. No. 847,676.
  • crystallinity of polymers is expressed as an order factor which is the same as the percentage crystallinity described in specification No. 847,676 except that it is the average value of the percentage crystallinities determined at 50C, C, C and 140C and that in the calculation of each percentage crystallinity the small area at G is ignored in calculating the value of X.
  • the crystallinity of a vinyl chloride polymer as mea sured by its order factor depends to a great extent upon the temperature at which it was formed by free radical polymerisation of the vinyl chloride monomer.
  • Conventional free radical processes for the manufacture of vinyl chloride polymers which are capable of being carried out on an industrial scale usually require a polymerisation temperature between 30 and 80C and, most suitably between 43 and 70C.
  • Such processes usually provide vinyl chloride polymers having order factors in the range 10 to 16.
  • the order factors of a number of commercially available vinyl chloride polymers are given in Table 1.
  • Breon 115, 113, and 107 are made by BP Chemicals International Limited (U.K.); Corvic D50/16 is made by lmperial Chemicals Industry Limited (U.K.); Lucovyl GB8010 is made by Pechiney-Saint Gobain (France); Pevikon KL-2 is made by Kema-Nord (Sweden); and Vestolit G is made by Chemische Werke Huls A. G. (W. Germany).
  • An object of the present invention is to provide a pro cess for the production of a vinyl chloride polymer having an order factor above 16 or below 10 using a conventional free radical polymerisation process Le, a process carried out at a temperature between 30 and 80C.
  • the present invention is a process for the production of a vinyl chloride polymer (as herein defined) which comprises adding a seed vinyl chloride polymer in a finely divided form having an order factor above 16 or below respectively to vinyl chlorode monomer (as herein defined) and polymerising the vinyl chloride monomer in suspension or in mass under free radical polymerisation conditions with said seed polymer dispersed therein at a temperature in the range 30 80C to produce a vinyl chloride polymer having an order factor above 16 or below 10 respectively.
  • the seed vinyl chloride polymer is in a finely divided form when it is added to the vinyl chloride monomer.
  • finely divided is meant that the vinyl chloride polymer particles have an average size preferably less than 200 ,um.
  • the size of the seed polymer particles is below 100 um and generally the best results are obtained with vinyl chloride polymer seeds having a particle size below 10 pm.
  • the polymerisation techniques described above for the preparation of more crystalline or less crystalline polymers can readily be adapted so that the product is in a suitably finely divided form.
  • the finely divided seed polymer may be added to the monomer and distributed therein by any suitable means.
  • the precise technique adopted will depend to a great extent on the method used for the production of the seed polymer and the form in which the seed polymer is produced. For example if the seed polymer is produced by mass polymerisation it is usually most convenient to stop the polymerisation at an early stage so as to produce the finely divided seed polymer directly in vinyl chloride monomer.
  • This mixture of seed polymer and monomer can then be polymerised under conventional free radical polymerisation conditions either as a mass process or suspension process.
  • the unconventional polymerisation conditions which give rise to a seed polymer having the desired order factor can be withdrawn before the polymerisation of the monomer is complete.
  • the polymerisation of the monomer can then be continued most suitably under suspension conditions using conventional free radical polymerisation conditions.
  • More vinyl chloride monomer and copolymerisable monomers if desired can be added to the system when the conventional polymerisation process is commenced.
  • emulsion or suspension polymerisation to produce the desired seed polymer may be carried to completion under the special polymerisation conditions in order to produce the seed as a suspension or emulsion polymer. This polymer can then be added to a conventional suspension polymerisation to provide a process according to the present invention.
  • seed polymer produced by emulsion or suspension techniques it may be necessary to dry the seed polymer before adding it to a mass polymerisation system.
  • various techniques can be employed. i.e., the addition of miscible or immiscible liquids to the system in order to precipitate the seed polymer in the desired finely divided form.
  • the final stage of the process of the present invention i.e., the conventional free radical polymerisation of the vinyl chloride monomer may be carried out using the well known suspension or mass vinyl chloride polymerisation techniques. Emulsion polymerisation is found to be unsatisfactory for the final stage of the process. As stated above most conventional vinyl chloride polymerisation techniques are operated between 30 and C and it is preferred to operate the second stage ofthe process of the present invention at a temperature in this range.
  • the order factor of the final product will be similar to that of the seed.
  • the seed polymer is more expensive than the final product to produce owing to the specialist polymerisation technique that must be used for its production, it is economically desirable to employ only sufficient quantity of seed polymer to impart the desired crystallinity to the final product.
  • the minimum quantity of seed required varies considerably depending on the nature of the seed and the polymerisation to be seeded. In some cases it may be as low as 0.1% but is generally of the order of 05-592.
  • the quantity of seed polymer employed can be varied widely, for example the weight ratio of seed polymer to monomer can be in the range 01:99.9 to 50:50 or preferably in the range 05:99.5 to 20:80. It is particularly preferred to use a ratio of seed polymer to monomer in the range 5:95 to 10:90.
  • Polymers of unusually high and low order factors have properties which differ from conventional vinyl chloride polymers. Polymers of low order factor for ex ample have lower softening points which tends to make them easier to process. but at the same time have generally a higher tensile yield strength and are stiffer (higher tensile modulus) than conventional polymers.
  • Polymers of high order factor are mere suitable for the production of fibres and filaments than conventional polymers.
  • Highly ordered vinyl chloride polymer has high thermal stability and higher softening point which makes it more suitable for applications where elevated temperatures are met with.
  • the process of the present invention is particularly suitable for producing vinyl chloride polymers having order factors in the ranges 16 to 25 and 4 to 10.
  • the seed resin was the resin prepared Table 5 by Example 1 l.
  • the Methocel 65HG 50 was dissolved in the distilled water and the solution poured into a 1 Example PVC/VC rat) Average gallon stainless steel container.
  • the seed resin and lau- Orcler Factor royl peroxlde were added and the reactor was closed,
  • the vinyl chloride was sucked l0 ⁇ g 3B 1&6 into the reactor.
  • the mixture was stirred at 700 rpm.
  • the Lauroy] peroxide lg lg product was separated from the aqueous phase by bas- Polymerisation Time 12 hours l0 hours ket centrifuge and washed with water in the centrifuge. The resin dried in a vacuum oven at 45C for 24 hours.
  • EXAMPLE l8 (45PVC/55VC) An experimental resin was made using a 1,000 gallon stainless steel reactor with the following recipe.
  • the latex was the same as that in Examples 4-8.
  • the powder was analysed by X'ray diffraction and the average total order factor was 7.7.
  • the resins were mixed with 2.5 p.h.r. of Mellite 31 a dibutyl thio stabiliser and stearic acid as shown.
  • the powder mixes were milled into hides at a temperature of 160/ 140C and then compression moulded into test pieces at 180C. Vicat softening points were measured according to BS2782 Part 1, 1965, Method 102D and the results are shown in the following table.
  • Test pieces 2.10 in X 0.03 in X 0.212 in were compression moulded at 180C and pulled on an Instron tensile test machine at 22C. The results were as follows.
  • the resins were made with the following recipe Vinyl chloride 700 g Copolymer seed varied Distilled water 2,800 g The weight of copolymer seed was varied and these weights are shown in Table 10.
  • the vinyl chloride was sucked into the reactor and the charge stirred at 700 r.p.m. The charge was heated at C for 8 hours.
  • the resin was dried in a vacuum oven at 45C for 24 hours.
  • the powders were analysed by X-ray diffraction and the average order factors are shown in Table 11.
  • COMPARATIVE TEST 22 A suspension resin was made by incorporating a mass resin as seed. The mass resin had been synthesized at 20C using a 25 ml. bomb. The average order factor of this resin was 18.6.
  • the suspension resin was made with the following recipe.
  • a solution of the Methocel 65HG 50 in the distilled water was charged, together with the mass resin and the lauroyl peroxide to a 1 gallon stainless steel reactor.
  • the reactor was closed, purged with nitrogen and evacuated.
  • the vinyl chloride was sucked into the reactor.
  • the mixture was stirred at 700 r.p.m. and heated at 60C for 15 hours.
  • the product was separated from the aqueous phase by basket centrifuge and washed with water in the centrifuge.
  • the resin was dried in a vacuum oven at 45C for 24 hours.
  • the powder was analysed by X-ray diffraction and the average order factor was 13.9.
  • the average order factor of the mass resin seed was 18.3 and the average order factor of the suspension resin was 19.0.
  • COMPARATIVE TEST 24 (2PVC/100VC) A suspension resin was made by a similar procedure to that adopted in Example 22. The recipe was Vinyl chloride 100 g Mass resin seed 2 g Methocel 65HG 50 2 g Distilled water 3.000 g Lauroyl peroxide 0.2 g
  • the average order factor of the mass resin seed was 18.2 and the average order factor of the suspension resin was 14.7.
  • EXAMPLE 25 (l0PVC/l00VC) A suspension resin was made by a similar procedure to that adopted in Example 22. The recipe was Vinyl chloride 100 g Mass resin seed 10 g Distilled water 3,000 g Methocell 65HG 50 2 g Lauroyl Peroxide 0.2 g
  • the seed resin was made by suspension polymerisation at a temperature of 20C.
  • the initiators and seed were put into a 1 gallon stainless steel reactor which was then closed and evacuated.
  • the vinyl chloride was added and the contents stirred at 30 rpm.
  • the reactor was heated at 54C for 2 hours and then cooled and the mixture was vented to atmosphere.
  • a process for the production of a vinyl chloride polymer containing a major proportion of vinyl chloride which comprises adding a seed vinyl chloride polymer or copolymer containing a major proportion of vinyl chloride in a finely divided form having an average particle size of less than 200 um and having an order factor above 16 or below 10, said seed polymer not having been prepared by a process defined in this claim, to vinyl chloride monomer and polymerising at a temperature in the range of 30-80C the vinyl chloride monomer in suspension or in mass using a free radical polymerisation initiator with said seed polymer or copolymer dispersed therein to produce a vinyl chlo ride containing polymer having an order factor above 16 or below 10, respectively, the weight ratio of said 14 polymerisation.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymerisation Methods In General (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Graft Or Block Polymers (AREA)
US00245193A 1971-04-21 1972-04-18 Polymerisation process Expired - Lifetime US3856767A (en)

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BE (1) BE782523A (xx)
CA (1) CA984547A (xx)
CH (1) CH537958A (xx)
DD (1) DD98291A5 (xx)
DE (1) DE2219402A1 (xx)
ES (1) ES401914A1 (xx)
FR (1) FR2133994B1 (xx)
GB (1) GB1378391A (xx)
IT (1) IT953325B (xx)
NL (1) NL7205408A (xx)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4031299A (en) * 1975-04-11 1977-06-21 Stauffer Chemical Company Process for forming a polyvinyl chloride extender resin by incorporating in the suspension polymerization medium a prehomogenized solution of a polyallyl compound and a low molecular polymer of propylene
US4093794A (en) * 1972-07-21 1978-06-06 Plastimer Process for the polymerization of vinyl chloride

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NO841494L (no) * 1983-04-21 1984-10-22 Conoco Inc Fremgangsmaate for fremstilling av pvc-harpiks
ATE283291T1 (de) * 2001-06-15 2004-12-15 Saudi Basic Ind Corp Verfahren zur herstellung von hautfreiem pvc

Citations (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB847676A (en) * 1957-10-30 1960-09-14 Ici Ltd Process for the polymerisation of vinyl chloride
US3067186A (en) * 1959-07-11 1962-12-04 Distillers Co Yeast Ltd Vinyl chloride polymerisation process
US3332918A (en) * 1962-12-21 1967-07-25 Edison Soc Vinyl chloride seed technique polymerization using emulsifying systems comprising two ammonium salts of different sulphocarboxylic acid esters
US3380946A (en) * 1965-10-22 1968-04-30 Pittsburgh Plate Glass Co Polymerization using peroxycarbonate esters with salts of sulfurous acid
US3520867A (en) * 1967-09-28 1970-07-21 Chatillon Italiana Fibre Process for the polymerization of vinyl chloride
US3523111A (en) * 1967-08-18 1970-08-04 Monsanto Co Emulsion polymerization of vinyl chloride with redox initiator system components and emulsifier prepared before monomer addition
US3536675A (en) * 1966-04-22 1970-10-27 Pechiney Saint Gobain Process of polymerizing vinyl chloride in suspension
US3652525A (en) * 1968-06-17 1972-03-28 Sumitomo Chemical Co Method for producing polyvinylchloride particles
US3683051A (en) * 1968-03-05 1972-08-08 Pechiney Saint Gobain Copolymers of vinyl chloride and lower olefins
US3687917A (en) * 1969-08-22 1972-08-29 Basf Ag Homopolymerization or copolymerization of vinyl chloride in the absence of solvents or dispersing agents
US3725375A (en) * 1969-05-19 1973-04-03 Bp Chem Int Ltd Polymerization process

Patent Citations (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB847676A (en) * 1957-10-30 1960-09-14 Ici Ltd Process for the polymerisation of vinyl chloride
US3067186A (en) * 1959-07-11 1962-12-04 Distillers Co Yeast Ltd Vinyl chloride polymerisation process
GB931629A (en) * 1959-07-11 1963-07-17 Distillers Co Yeast Ltd Vinyl chloride polymerisation process
US3332918A (en) * 1962-12-21 1967-07-25 Edison Soc Vinyl chloride seed technique polymerization using emulsifying systems comprising two ammonium salts of different sulphocarboxylic acid esters
US3380946A (en) * 1965-10-22 1968-04-30 Pittsburgh Plate Glass Co Polymerization using peroxycarbonate esters with salts of sulfurous acid
US3536675A (en) * 1966-04-22 1970-10-27 Pechiney Saint Gobain Process of polymerizing vinyl chloride in suspension
US3523111A (en) * 1967-08-18 1970-08-04 Monsanto Co Emulsion polymerization of vinyl chloride with redox initiator system components and emulsifier prepared before monomer addition
US3520867A (en) * 1967-09-28 1970-07-21 Chatillon Italiana Fibre Process for the polymerization of vinyl chloride
US3683051A (en) * 1968-03-05 1972-08-08 Pechiney Saint Gobain Copolymers of vinyl chloride and lower olefins
US3652525A (en) * 1968-06-17 1972-03-28 Sumitomo Chemical Co Method for producing polyvinylchloride particles
US3725375A (en) * 1969-05-19 1973-04-03 Bp Chem Int Ltd Polymerization process
US3687917A (en) * 1969-08-22 1972-08-29 Basf Ag Homopolymerization or copolymerization of vinyl chloride in the absence of solvents or dispersing agents

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
J.P.S. 41, p. 79 81, 1959. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4093794A (en) * 1972-07-21 1978-06-06 Plastimer Process for the polymerization of vinyl chloride
US4031299A (en) * 1975-04-11 1977-06-21 Stauffer Chemical Company Process for forming a polyvinyl chloride extender resin by incorporating in the suspension polymerization medium a prehomogenized solution of a polyallyl compound and a low molecular polymer of propylene

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DE2219402A1 (de) 1972-11-02
ZA722579B (en) 1973-11-28
CA984547A (en) 1976-02-24
DD98291A5 (xx) 1973-06-12
FR2133994B1 (xx) 1976-10-29
BE782523A (fr) 1972-10-23
ES401914A1 (es) 1975-04-16
GB1378391A (en) 1974-12-27
AU4138372A (en) 1973-10-25
IT953325B (it) 1973-08-10
NL7205408A (xx) 1972-10-24
FR2133994A1 (xx) 1972-12-01
SE400297B (sv) 1978-03-20
CH537958A (fr) 1973-06-15

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